CN108138032A - Composition for polishing - Google Patents

Composition for polishing Download PDF

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Publication number
CN108138032A
CN108138032A CN201680061350.6A CN201680061350A CN108138032A CN 108138032 A CN108138032 A CN 108138032A CN 201680061350 A CN201680061350 A CN 201680061350A CN 108138032 A CN108138032 A CN 108138032A
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China
Prior art keywords
composition
polishing
polyalcohol
weight
haze value
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Granted
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CN201680061350.6A
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Chinese (zh)
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CN108138032B (en
Inventor
杉田规章
松田修平
松下隆幸
知念美佳
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Nitta DuPont Inc
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Nitta Haas Inc
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02002Preparing wafers
    • H01L21/02005Preparing bulk and homogeneous wafers
    • H01L21/02008Multistep processes
    • H01L21/0201Specific process step
    • H01L21/02024Mirror polishing
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09GPOLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00Polishing compositions
    • C09G1/02Polishing compositions containing abrasives or grinding agents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B24GRINDING; POLISHING
    • B24BMACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B37/00Lapping machines or devices; Accessories
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00Materials not provided for elsewhere
    • C09K3/14Anti-slip materials; Abrasives
    • C09K3/1454Abrasive powders, suspensions and pastes for polishing
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304Mechanical treatment, e.g. grinding, polishing, cutting
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/30625With simultaneous mechanical treatment, e.g. mechanico-chemical polishing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B24GRINDING; POLISHING
    • B24BMACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B37/00Lapping machines or devices; Accessories
    • B24B37/04Lapping machines or devices; Accessories designed for working plane surfaces
    • B24B37/042Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor
    • B24B37/044Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor characterised by the composition of the lapping agent

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)
  • Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)

Abstract

The present invention provides the composition for polishing of a kind of inhibition of achievable surface defect and the reduction of mist degree.Composition for polishing includes abrasive grain, selected from least one of the vinyl alcohol resin with 1,2 diol structure unit water soluble polymer, polyalcohol and alkali cpd.Composition for polishing preferably further includes nonionic surfactant.

Description

Composition for polishing
Technical field
The present invention relates to a kind of composition for polishing.
Background technology
Grinding using the silicon wafer of CMP (Chemical Mechanical Polishing, chemical mechanical grinding) passes through It carries out the multistage grinding in 3 stages or 4 stages and realizes high-precision planarization.For the institute in the grinding process of terminal stage The slurry used, usually using the water soluble polymers such as hydroxyethyl cellulose (HEC) and polyvinyl alcohol (PVA).
For example, having following composition for polishing disclosed in Japanese Patent Laid-Open 2012-216723 bulletins, it includes choosings From at least one kind of water soluble polymer and alkali in the vinyl alcohol resin with 1,2- diol structure units.
Invention content
However, in recent years, it is desirable that with the tightened up horizontal mist degree (haze) for inhibiting surface defect, reducing surface.
The present invention completes in order to solve this problem, and grinding for surface defect and mist degree is reduced its purpose is to provide a kind of Mill composition.
Implementation form according to the present invention, composition for polishing include abrasive grain, selected from 1 represented by following formula (1), At least one kind of water soluble polymer, polyalcohol and alkali cpd in the vinyl alcohol resin of 2- diol structure units.
In formula, R1、R2And R3Separately represent hydrogen atom or organic group, X represents singly-bound or key chain, R4、R5And R6 Separately represent hydrogen atom or organic group, R7And R8Separately represent hydrogen atom.
Implementation form according to the present invention, composition for polishing include abrasive grain, selected from 1 represented by above-mentioned formula (1), At least one kind of water soluble polymer, polyalcohol and alkali cpd in the vinyl alcohol resin of 2- diol structure units, therefore The inhibition of surface defect of silicon wafer after grinding and the reduction of mist degree can be achieved.
Specific embodiment
The implementation form of the present invention is described in detail.
The composition for polishing COMP1 of the implementation form of the present invention includes abrasive grain, selected from represented by following formula (1) At least one kind of water soluble polymer, polyalcohol and alkali cpd in the vinyl alcohol resin of 1,2- diol structure unit.
[chemical formula 1]
In formula, R1、R2And R3Separately represent hydrogen atom or organic group, X represents singly-bound or key chain, R4、R5And R6 Separately represent hydrogen atom or organic group, R7And R8Separately represent hydrogen atom.
Composition for polishing COMP1 is used for the grinding of silicon.
As abrasive grain, common abrasive grain in the field can be used, such as colloidal silicon dioxide, gas phase titanium dioxide can be enumerated Silicon, colloidal alumina, gaseous oxidation aluminium and cerium oxide etc., particularly preferably colloidal silicon dioxide or aerosil.
Water soluble polymer represented by above formula (1) is modified polyvinylalcohol (modified PVA).As modified PVA, can make With the PVA of high saponification type, the PVA of low saponification type can also be used.In addition, as modified PVA, the arbitrary degree of polymerization can be used PVA.As modified PVA, it is independently matched with a kind or coordinates two or more.
It's not limited to that for the content of water soluble polymer, with relative to the weight % of abrasive composition (stoste) entirety Meter, preferably for example, 0.01~1.0 weight %, 0.03~0.7 weight %.In addition, with relative to the ratio of 1 parts by weight of abrasive grain Meter, preferably for example, 0.001~0.1 parts by weight, 0.003~0.07 parts by weight.
Polyalcohol is the alcohol that 2 or more hydroxyls are included in 1 molecule.As polyalcohol, such as can enumerate:Sugar with sugar with It is glucosides (Glycoside) obtained by glycoside link occurs for outer organic compound, more obtained by addition alkylene oxide on polyalcohol It is polyol esters of fatty acids obtained by ester linkage occurs for first alcohol alkylene oxide addition product, aliphatic acid and polyalcohol, glycerine, propylene glycol, poly- Ethylene glycol etc..As glucosides, such as alkylene oxide derivative of methyl glucosamine represented by following formula (2) etc. can be enumerated.As more First alcohol alkylene oxide addition product, such as the alkylene oxide addition product of glycerine, pentaerythrite, ethylene glycol etc. can be enumerated.As polyol resin Fat acid esters, such as fatty glyceride, aliphatic acid sorbitol ester, sorbitan fatty esters, aliphatic acid sugarcane can be enumerated Sugar ester etc..Polyhydric alcohols are coordinated such as the use level less than water soluble polymer.
[chemical formula 2]
In formula, AO represents alkylene oxide.In addition, a~d represents integer.
As the alkylene oxide derivative of methyl glucosamine, such as polyoxyethylene methyl glucosamine, polyoxy Asia third can be enumerated Ylmethyl glucoside etc..
As polyalcohol, a kind can be used, can also be used together by two or more types.It may refrain from surface defect and reduce the sight of mist degree For point, preferably polyhydric alcohol conjugate of more than two kinds is used.
It's not limited to that for the content (in the case of containing two or more polyalcohol, the content total for its) of polyalcohol, By based on the weight % of abrasive composition (stoste) entirety, for example, 0.0001~0.3 weight %, preferably 0.001~ 0.1 weight %.In addition, by based on the ratio of 1 parts by weight of abrasive grain, for example, 0.00001~0.03 parts by weight, preferably 0.0001~0.01 parts by weight.
As alkali cpd, ammonia, quarternary ammonium salt, potassium hydroxide, sodium hydroxide, saleratus, potassium carbonate, carbonic acid can be enumerated Hydrogen sodium, sodium carbonate, ammonium hydrogen carbonate, ammonium carbonate, amine compounds etc..As alkali cpd, these illustrated changes can be independently matched with 1 kind in object is closed, two or more can also be coordinated.As quarternary ammonium salt, such as tetramethyl ammonium hydroxide, hydroxide four can be enumerated Ethyl ammonium etc..
It should be noted that as amine compounds, aliphatic amine, hetero ring type amine etc. can be coordinated.Specifically, it can coordinate Methyl amine, dimethyl amine, Trimethylamine, ethylamine, diethylamide, triethylamine, propyl amine, butylamine, hexyl amine, cyclohexyl Amine, ethylenediamine, hexamethylene diamine, diethylenetriamines, trien, ethanol amine, Piperazine anhydrous, piperazine six are hydrated Object, 1- (2- amidos ethyl) piperazine and N methyl piperazine etc..
It's not limited to that for the content of alkali cpd, by based on the weight % of abrasive composition (stoste) entirety, example Such as it is 0.001~1.0 weight %, preferably 0.01~0.7 weight %.In addition, by based on the ratio of 1 parts by weight of abrasive grain, For example, 0.0001~0.1 parts by weight, preferably 0.001~0.07 parts by weight.
Composition for polishing COMP1 will be by that will be selected from the second with 1, the 2- diol structure units represented by above-mentioned formula (1) At least one kind of water soluble polymer, abrasive grain, polyalcohol and alkali cpd in enol system resin suitably mix and add water It makes.In addition, composition for polishing COMP1 passes through successively by abrasive grain, selected from 1, the 2- glycol knots represented by above-mentioned formula (1) At least one kind of water soluble polymer, polyalcohol and alkali cpd in the vinyl alcohol resin of structure unit are mixed in water to make Make.Also, as the method mixed these ingredients, the skill of the composition for polishing such as homogenizer and ultrasonic wave can be used Common method in art field.
Composition for polishing COMP1 includes alkali cpd, and as a result such as pH value is set at 8~12 range.
Composition for polishing COMP1 preferably further includes nonionic surfactant.It lives as non-ionic surface Property agent, such as the diamine compound preferably represented by the following general formula (3).Diamine compound represented by general formula (3) includes tool There is the Alkylenediamine structure of 2 nitrogen and be bonded at least one block type polyethers on 2 nitrogen of Alkylenediamine structure, it is embedding Segment type polyethers is obtained by oxygen ethylidene is bonded with oxygen propylidene
[chemical formula 3]
In formula, n represents more than 1 integer.
As the diamine compound represented by formula (3), such as N, N, N ' can be enumerated, (polyoxy is sub- by N '-four (polyoxyethylene) Propyl) ethylenediamine (that is, pool Lip river sand amine) etc..Lip river sand amine is moored for example to be represented by following formula (4) or formula (5).
[chemical formula 4]
In formula, a~g represents integer.
[chemical formula 5]
In formula, a~g represents integer.
As nonionic surfactant, other than the diamine compound represented by formula (3), pool Lip river can also be used Sha Mu, polyoxyalkylene alkyl ether, polyoxyalkylene fatty acid esters, amines etc..
As polyoxyalkylene alkyl ether, for example, can enumerate polyoxyethylenelauryl ether, polyoxyethylene cetyl ether, Polyoxyethylene stearyl ether etc..As polyoxyalkylene fatty acid esters, such as polyoxyethylene monolaurate can be enumerated, gathered Oxygen ethylidene monostearate etc..As amines, such as polyoxyethylenelauryl base amine, polyoxy Asia can be enumerated Ethyl oil base amine etc..
It's not limited to that for the content of nonionic surfactant, with relative to the weight of abrasive composition (stoste) entirety Measure % meters, preferably for example, 0.0001~0.3 weight %, 0.001~0.1 weight %.In addition, with relative to 1 weight of abrasive grain The ratio meter of part, preferably for example, 0.00001~0.03 parts by weight, 0.0001~0.01 parts by weight.
In the implementation form of the present invention, composition for polishing COMP1 can further include chela according to required characteristic Mixture, acidic materials etc..
As chelating agent, such as amido carboxylic serials chelating agent and organic phospho acid system chelating agent etc. can be enumerated.
As amido carboxylic serials chelating agent, such as ethylenediamine tetra-acetic acid, sodium ethylene diamine tetracetate, three second of nitrilo- can be enumerated Acid, sodium nitrilo triacetate, nitrilotriacetic acid ammonium, Oxyethylethylenediaminetriacetic acid, Oxyethylethylenediaminetriacetic acid sodium, Diethylene-triamine pentaacetic acid, diethylenetriaminepentaacetic acid sodium, triethylenetetraaminehexaacetic acid, triethylenetetraaminehexaacetic acid Sodium etc..
As organic phospho acid system chelating agent, such as 2- amidos ethylphosphonic acid, 1- hydroxy ethylidene base -1,1- diphosphines can be enumerated Acid, amido three (methylene phosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid), diethylene triamine penta(methylene phosphonic acid), ethane -1, 1,-di 2 ethylhexyl phosphonic acid, ethane -1,1,2- tri methylene phosphonic acids, ethane -1- hydroxyls -1,1- di 2 ethylhexyl phosphonic acid, ethane -1- hydroxyls -1,1,2- tri methylene phosphonic acids, Ethane -1,2- dicarboxyl -1,2- di 2 ethylhexyl phosphonic acid, methane hydroxyethylidene diphosphonic acid, 2- phosphinylidyne butanes -1,2- dicarboxylic acids, 1- phosphinylidyne butanes - 2,3,4- tricarboxylic acids, Alpha-Methyl phosphonosuccinic acid etc..
As acidic materials, carboxylate, sulfonate, acid phosphate salt, phosphonate, inorganic acid salt, alkylamine can be enumerated Ethylene oxide adduct, polyol partial esters, carboxylic acid amide etc..
More than, above-mentioned implementation form is only the example for being used for implementing the present invention.Therefore, the present invention is not limited to above-mentioned implementations Above-mentioned implementation form can be suitably changed in and implement by form within the scope of its spirit.
Embodiment
Hereinafter, explain the present invention in detail with embodiment.Specifically, conduct the following evaluation 1~evaluation test of experiment 9。
<Evaluation test 1>(embodiment 1, comparative example 1)
The composition for polishing Sample 1 of embodiment 1 is by abrasive grain (colloidal silicon dioxide), 0.5 weight of 9.5 weight % Measure the ammonium hydroxide (NH of %4OH), modified PVA (degree of polymerization of 0.0135 weight %:450), the polyalcohol of 0.015 weight % (1) it is matched in water and will integrally be set as obtained by 100 parts by weight.
The average primary particle diameter (BET (Brunauer-Emmett-Teller) method) of abrasive grain as used herein is 35nm, Average aggregate particle size is 70nm.In addition, polyalcohol (1) is polyoxyethylene methyl glucosamine, molecular weight 634.
The composition for polishing Sample_CP1 of comparative example 1 is in addition to by the modified PVA of the composition for polishing of embodiment 1 Use level be set as 0.15 weight %, and then other than unmated polyalcohol (1), composition same as Example 1.
As the composition for polishing Ref_1 of reference example, composition for polishing (NP8020H, the Nitta of commercially available product are used Haas Co., Ltd. manufactures).
It should be noted that above-mentioned composition is the composition before dilution, it is diluted and uses in grinding.In the present embodiment In comparative example, further add 20 parts by weight of water (that is, being diluted to 21 times) relative to 1 parts by weight of stoste and use (under It states embodiment and comparative example and is also set as identical).About the composition for polishing Ref_1 of reference example, following evaluation tests 2 with Identical composition for polishing is also used afterwards.
The ingredient of the composition for polishing of embodiment 1, comparative example 1 and reference example is shown in table 1.In table 1, each ingredient Weight % represents the weight % relative to composition for polishing (stoste) entirety (for being also set as identical after table 2).
For the composition for polishing of above-described embodiment 1, comparative example 1 and reference example, ground with following grinding condition Mill.Also, carry out the measure of defect number and haze value.
(grinding condition)
It, will implementation with the ratio of 600mL/ minute using grinding device (SPP800S, this work mechanism of ridge make manufactured by) The composition for polishing of example 1 and comparative example 1 is supplied to grinding pad (manufacture of SUPREME RN-H, Nitta Haas Co., Ltd.), Carry out the grinding of 5 minutes silicon wafers.Used silicon wafer is the P-type semiconductor of a diameter of 300mm, and crystal orientation is (100). As grinding condition at this time, grinding pressure 0.012MPa, the rotary speed for grinding platen is 40rpm, and the rotation of carrier is fast It spends for 39rpm.
(defect number assay method)
For above-described embodiment 1 and comparative example 1, checking device (the Lasertec Co. Ltd. systems of wafer defect detecting/again are used Make MAGICS series, M5640) carry out defect number measure.Determination condition is D37mV.It should be noted that the survey of defect number It is also identical in following embodiments and comparative example to determine method.
(mist degree values determination method)
For above-described embodiment 1 and comparative example 1, wafer surface check device (Hitachi Electronics are used Engineering Co., Ltd. manufacture, LS6600) carry out haze value measure.It should be noted that the assay method of haze value Also it is identical in following embodiments and comparative example.
Will be measured by this method the defects of number and the result of haze value be shown in table 1.It should be noted that by reference example The measurement result of defect number and haze value is set as 100 and represents embodiment 1 and the measurement result of comparative example 1 with relative value.
[table 1]
(evaluation of embodiment)
By the comparison of embodiment 1 and comparative example 1 it is found that a part for the content of modified PVA is replaced into polyalcohol (1) Embodiment 1 in, defect number, haze value significantly reduce.It is considered that modified PVA protection chip surface, and with pair The surface of chip assigns the function of wetability.In contrast, as the composition for polishing for including both modified PVA and polyalcohol The reasons why superior defect number and haze value can be obtained, it is believed that polyalcohol, therefore can be with than modified PVA molecular weight smaller The surface of chip is more densely protected than modified PVA.
<Evaluation test 2>(embodiment 2~3, comparative example 2)
The composition for polishing Sample 2 of embodiment 2 is by abrasive grain (colloidal silicon dioxide), 0.27 weight of 9.5 weight % Measure the ammonium hydroxide (NH of %4OH), the modified PVA of 0.07 weight %, 0.014 weight % polyalcohol (1) be matched in water simultaneously It will integrally be set as obtained by 100 parts by weight.
The composition for polishing Sample 3 of embodiment 3 is in addition to the polyalcohol (2) of 0.014 weight % of cooperation replaces implementing Other than the polyalcohol (1) coordinated in the composition for polishing of example 2, composition same as Example 2.
Polyalcohol (2) as used herein is polyoxypropylene methyl glucosamine, molecular weight 774.
The composition for polishing Sample_CP2 of comparative example 2 is in addition to the pool Lip river sand amine of 0.014 weight % of cooperation replaces in fact It applies other than the polyalcohol (1) coordinated in the composition for polishing of example 2, composition same as Example 2.
It should be noted that it is used herein as an example of the pool Lip river sand amine as nonionic surfactant.Specifically, make To moor Lip river sand amine, the inverse pool Lip river sand amine represented by using following formula (4).The EO/PO ratios (weight ratio) of the pool Lip river sand amine are 40/60, Molecular weight is 6900.
[chemical formula 4]
In formula, a~g represents integer.
The ingredient of embodiment 2~3 and the composition for polishing of comparative example 2 is shown in table 2.
For the composition for polishing of above-described embodiment 2~3, comparative example 2 and reference example, with embodiment 1 and comparative example 1 Identical grinding condition is ground.Also, carry out the measure of defect number and haze value.Will be measured the defects of number and haze value Result be shown in table 2.Herein, the measurement result of number the defects of reference example and haze value is set as 100 and represents real with relative value Apply example 2~3 and the measurement result of comparative example 2.
[table 2]
(evaluation of embodiment)
According to embodiment 2~3 and comparative example 2, compared with comparative example 2, defect number, haze value significantly drop embodiment 2 and 3 It is low.It follows that in the composition for polishing comprising abrasive grain, modified PVA, polyalcohol and ammonium hydroxide, polyalcohol is had Surface characteristic improvement effect be more than pool Lip river sand amine possessed by surface characteristic improvement effect.
If embodiment 2 and embodiment 3 are compared, the reality of the polyalcohol (1) as epoxyethane derivative is included It is less than the 3 defect number of embodiment comprising the polyalcohol (2) as propylene oxide derivatives to apply example 2.On the other hand, comprising conduct Embodiment of the embodiment 3 of the polyalcohol (2) of propylene oxide derivatives than including the polyalcohol (1) as epoxyethane derivative 2 haze values are lower.I.e., it is known that the polyalcohol of ethylene system more effectively plays a role to defect number, and the polyalcohol of propylene is to mist Degree more effectively plays a role.
Polyalcohol about propylene more effectively plays a role to haze value this point compared to the polyalcohol of ethylene system, It is believed that the difference of the etching inhibition of the compound of the compound and propylene of ethylene system causes influence.
Past, present inventor et al. studies the etching inhibiting effect of alkali cpd, as a result obtains propylene Compound is compared to the opinion of the compound etching inhibiting effect bigger of ethylene system.If the opinion is examined applied to polyalcohol Consider, it may be considered that the polyalcohol of propylene etches inhibiting effect bigger compared to the polyalcohol of ethylene system.That is, include propylene Polyalcohol composition for polishing compared with the composition for polishing of the polyalcohol comprising ethylene system, be not easy carry out by grinding use The etching on the surface of the chip caused by composition.Thus, it is believed that the mist of the index of surface roughness ingredient as chip Angle value reduces.
Polyalcohol about ethylene system more effectively plays a role to defect number this point compared to the polyalcohol of propylene, It is directly affected it is believed that composition for polishing causes the degree of absorption of wafer surface.
If composition for polishing becomes larger to the adsorption capacity of wafer surface, usual mechanical abrasive action is suppressed.Therefore, The generation of the damage to wafer surface caused by mechanical lapping is inhibited.In addition, composition for polishing is adsorbed in chip Surface and protect wafer surface, so as to which particle be inhibited to be attached to the surface of chip.On the other hand, if composition for polishing is to chip The adsorption capacity on surface becomes larger, then has grinding rate reduction, removes the damage suffered by wafer surface (especially to the relatively deep of wafer face Damage) the tendency that dies down of power.
Composition for polishing for the compound comprising ethylene system and the grinding of the compound comprising propylene are with combining For object, the composition for polishing of the compound comprising propylene is larger to the adsorption capacity of wafer surface.It is believed that it is tried in evaluation It tests in 2, embodiment 3 is more firmly adsorbed in the surface of chip than the composition for polishing of embodiment 2, and grinding rate reduces, knot Fruit, the power for removing the deeper damage for being present in wafer surface weakens, so as to which defect number increases than embodiment 2.
<Evaluation test 3>(embodiment 4~6)
The Sample 4 of embodiment 4 is in addition to being further combined with 0.0040 weight in the composition for polishing of comparative example 2 Other than the polyalcohol (1) for measuring %, the composition identical with comparative example 2.
The Sample 5 of embodiment 5 is in addition to the use level of the polyalcohol (1) of the composition for polishing of embodiment 4 is set as Other than 0.0021 weight %, composition same as Example 4.
The Sample 6 of embodiment 6 is in addition to the polyalcohol (2) of 0.0021 weight % of cooperation is used instead of the grinding of embodiment 5 Other than the polyalcohol (1) of composition, composition same as Example 5.
The ingredient of the composition for polishing of embodiment 4~6 is shown in table 3.
For the composition for polishing of above-described embodiment 4~6 and reference example, with embodiment 1 and comparative example 1 are identical grinds Abrasive stick part is ground.Also, carry out the measure of defect number and haze value.Will be measured the defects of number and the result of haze value show In table 3.Herein, the measurement result of number the defects of reference example and haze value is set as 100 and embodiment 4~6 is represented with relative value Measurement result.
[table 3]
(evaluation of embodiment)
As embodiment 4 and 5 it is found that if the use level of polyalcohol included in composition for polishing (1) increases from embodiment 5 Embodiment 4 is added to, then defect number, haze value reduce.
If the embodiment 5 and 6 that pool Lip river sand amine is combined in composition for polishing is compared, with evaluation test 2 In embodiment 2 and 3 comparison similarly, 5 ratio of embodiment comprising the polyalcohol (1) as epoxyethane derivative includes work The 6 defect number of embodiment of polyalcohol (2) for propylene oxide derivatives is less.On the other hand, comprising deriving as propylene oxide The embodiment 6 of the polyalcohol (2) of object is lower than 5 haze value of embodiment comprising the polyalcohol (1) as epoxyethane derivative.
<Evaluation test 4>(embodiment 7~10)
In embodiment 7, the composition for polishing with the composition for polishing identical component used in embodiment 4 is used Sample 4。
The Sample 7 of embodiment 8 is in addition to the use level of the polyalcohol (1) of the composition for polishing of embodiment 7 is set as 0.002 weight % is further combined with other than the polyalcohol (2) of 0.002 weight %, composition same as Example 7.
The Sample 8 of embodiment 9 is in addition to being further combined with 0.004 weight in the composition for polishing of embodiment 7 Other than the polyalcohol (2) for measuring %, composition same as Example 7.
The Sample 9 of embodiment 10 is in addition to that will moor Lip river sand amine from the gradation composition of the composition for polishing of embodiment 9 Other than removal, composition same as Example 9.
The ingredient of the composition for polishing of embodiment 7~10 is shown in table 4.
(grinding condition)
For the composition for polishing of above-described embodiment 7~10, it is ground with following grinding condition.It is filled using grinding It puts (SPP800S, this work mechanism of ridge make manufactured by), with the ratio of 600mL/ minutes by the grinding group of embodiment 7~10 It closes object and supplies the grinding that 3 minutes silicon wafers are carried out to grinding pad (manufacture of SUPREME RN-H, Nitta Haas Co., Ltd.). Used silicon wafer is the P-type semiconductor of a diameter of 300mm, and crystal orientation is (100).As grinding condition at this time, grind Mill load is 0.010MPa, and the rotary speed for grinding platen is 50rpm, and the rotary speed of carrier is 52rpm.
These embodiments 7~10 and reference example are carried out with the measure of defect number and haze value.Will be measured the defects of number and The result of haze value is shown in table 4.Herein, the measurement result of number the defects of reference example and haze value is set as 100 and with relative value Represent the measurement result of embodiment 7~10.
[table 4]
(evaluation of embodiment)
If the equal embodiment 7 of the summation of the use level of polyalcohol is compared with embodiment 8, it is found that and with more The embodiment 8 of first alcohol (1) and polyalcohol (2) compared to being used alone polyalcohol (1) embodiment 7 as polyalcohol, defect number, Haze value is greatly lowered.
It is believed that it is further reduced as defect number if polyalcohol and haze value and if by the use of polyalcohol (1) and polyalcohol (2) The reason of be:By and with the polyalcohol of ethylene system and the polyalcohol of propylene, the polyalcohol institute of ethylene system is played well What is had makes the reduction of defect number the reduction possessed by the property of big contribution and the polyalcohol of propylene to haze value Make the property of big contribution both characteristics.
If as embodiment 8~9 it is found that the use level of polyalcohol included in composition for polishing (1) and polyalcohol (2) Increase, then haze value reduces.In addition, about herein the defects of number, embodiment 8, embodiment 9 show the value of same degree.
By embodiment 9~10 it is found that even if when composition for polishing includes 2 kinds of polyalcohols, in composition for polishing into one In the case that step is comprising pool Lip river sand amine, the effect for reducing defect number and haze value also increases.
<Evaluation test 5>(embodiment 11~16)
In embodiment 11, the composition for polishing with the composition for polishing identical component used in embodiment 8 is used Sample 7。
The Sample 10 of embodiment 12 is will pool Lip river sand in addition to from the gradation composition of the composition for polishing of embodiment 11 Other than amine removal, the composition identical with embodiment 11.
The Sample 11 of embodiment 13 is in addition to by the use level of the polyalcohol (2) of the composition for polishing of embodiment 12 It is set as other than 0.004 weight %, the composition identical with embodiment 12.
The Sample 12 of embodiment 14 is in addition to by the use level of the polyalcohol (1) of the composition for polishing of embodiment 12 It is set as other than 0.004 weight %, the composition identical with embodiment 12.
In embodiment 15, the composition for polishing with the composition for polishing identical component used in embodiment 10 is used Sample 9。
The Sample 13 of embodiment 16 is in addition to by the use level of the polyalcohol (1) of the composition for polishing of embodiment 12 0.010 weight % is set as, further the use level of polyalcohol (2) is set as other than 0.010 weight %, it is identical with embodiment 12 Composition.
The ingredient of the composition for polishing of embodiment 11~16 is shown in table 5.
For the composition for polishing of above-described embodiment 11~16 and reference example, with the grinding identical with embodiment 7~10 Condition is ground.Also, carry out the measure of defect number and haze value.Will be measured the defects of number and the result of haze value be shown in Table 5.Herein, the measurement result of number the defects of reference example and haze value is set as 100 and embodiment 11~16 is represented with relative value Measurement result.
[table 5]
(evaluation of embodiment)
By embodiment 11~12 it is found that further including the situation of pool Lip river sand amine in the composition for polishing comprising polyalcohol Under, reduce the effect increase of defect number and haze value.But if the embodiment 2~3 in consideration evaluation test 2 is compared with together The result of study of example 2, then it is believed that polyalcohol is with mooring in the sand amine of Lip river, polyalcohol significantly contributes to reduce defect number and mist degree Value.
By embodiment 12~16 it is found that even if in the system for including 2 kinds of polyalcohols in composition for polishing, if grinding group The sum of use level of polyalcohol (1) and polyalcohol (2) increase included in object is closed, then defect number, haze value also reduce.
It, can if the equal embodiment 13 and 14 of the sum of the use level of polyalcohol (1) and polyalcohol (2) is compared Know, the embodiment 14 that the ratio of the polyalcohol (1) of ethylene system is higher is less than 13 defect number of embodiment, the polyalcohol of propylene (2) the higher embodiment 13 of ratio becomes smaller than 14 haze value of embodiment.That is, confirm 2 He of embodiment for meeting evaluation test 2 The result of discussion in 3.
<Evaluation test 6>(embodiment 17~20)
In embodiment 17, the composition for polishing with the composition for polishing identical component used in embodiment 6 is used Sample 6。
The Sample 14 of embodiment 18 is in addition to being further combined with 0.014 weight in the composition for polishing of embodiment 2 Other than the pool Lip river sand amine for measuring %, composition same as Example 2.
In embodiment 19, the composition for polishing with the composition for polishing identical component used in embodiment 5 is used Sample 5。
The Sample 15 of embodiment 20 is in addition to the use level of the pool Lip river sand amine of the composition for polishing of embodiment 18 is set Other than 0.021 weight %, the composition identical with embodiment 18.
The ingredient of the composition for polishing of embodiment 17~20 is shown in table 6.
For the composition for polishing of above-described embodiment 17~20 and reference example, with the lapping stick identical with embodiment 4~6 Part is ground.Also, carry out the measure of defect number and haze value.Will be measured the defects of number and the result of haze value be shown in table 6.Herein, the measurement result of number the defects of reference example and haze value is set as 100 and embodiment 17~20 is represented with relative value Measurement result.
[table 6]
(evaluation of embodiment)
According to the comparison of embodiment 17 and embodiment 19, the implementation of the polyalcohol (1) as epoxyethane derivative is included Example 19 is less than the 17 defect number of embodiment comprising the polyalcohol (2) as propylene oxide derivatives.On the other hand, comprising conduct Implementation of the embodiment 17 of the polyalcohol (2) of propylene oxide derivatives than including the polyalcohol (1) as epoxyethane derivative Example 19 and haze value is lower.
It is lacked as embodiment 18 and 20 it is found that if the use level of Lip river sand amine is moored included in composition for polishing to be increased Fall into number, haze value reduces.
<Evaluation test 7>(embodiment 21~26, comparative example 3)
The Sample 16 of embodiment 21 is in addition to by the use level of the polyalcohol (1) of the composition for polishing of embodiment 18 It is set as other than 0.0007 weight %, the composition identical with embodiment 18.
In embodiment 22, the composition for polishing with the composition for polishing identical component used in embodiment 18 is used Sample 14。
The Sample 17 of embodiment 23 is in addition to by the use level of the polyalcohol (1) of the composition for polishing of embodiment 21 It is set as other than 0.0028 weight %, the composition identical with embodiment 21.
In embodiment 24, the composition for polishing with the composition for polishing identical component used in embodiment 4 is used Sample 4。
The Sample 18 of embodiment 25 is in addition to the use level of the pool Lip river sand amine of the composition for polishing of embodiment 22 is set Other than 0.007 weight %, the composition identical with embodiment 22.
In embodiment 26, the composition for polishing with the composition for polishing identical component used in embodiment 20 is used Sample 15。
In comparative example 3, the composition for polishing with the composition for polishing identical component used in comparative example 2 is used Sample_CP2。
The ingredient of embodiment 21~26 and the composition for polishing of comparative example 3 is shown in table 7.
For the composition for polishing of above-described embodiment 21~26, comparative example 3 and reference example, with identical with embodiment 4~6 Grinding condition be ground.Also, carry out the measure of defect number and haze value.Will be measured the defects of number and haze value knot Fruit is shown in table 7.Herein, the measurement result of number the defects of reference example and haze value is set as 100 and embodiment is represented with relative value 21~26 and the measurement result of comparative example 3.
[table 7]
(evaluation of embodiment)
Even by the comparison of embodiment 21~24 and comparative example 3 it is found that being combined with the composition for polishing of pool Lip river sand amine, The embodiment 21~24 of polyalcohol (1) is combined with compared with comparative example 3, defect number, haze value also significantly reduce.
It is lacked as embodiment 21~24 it is found that if the use level of polyalcohol included in composition for polishing (1) increases Fall into number, haze value reduces.
As embodiment 22,25 and 26 it is found that if the use level of Lip river sand amine is moored included in composition for polishing to be increased, Defect number, haze value reduce.
<Evaluation test 8>(embodiment 27~28)
The composition for polishing Sample 19 of embodiment 27 is by the hydroxide of the abrasive grain of 3.5 weight %, 0.1 weight % Ammonium (NH4OH), the pool Lip river sand amine of the modified PVA of 0.1 weight %, the polyalcohol (2) of 0.02 weight % and 0.01 weight % is matched Together in will be set as in water and integrally obtained by 100 parts by weight.
The Sample 20 of embodiment 28 is in addition to the use level of the abrasive grain of the composition for polishing of embodiment 27 is set as Other than 9.0 weight %, the composition identical with embodiment 27.
The ingredient of the composition for polishing of embodiment 29~30 is shown in table 8.
(grinding condition)
For the composition for polishing of above-described embodiment 29~30, it is ground with following grinding condition.Use grinding Device (SPP800S, this work mechanism of ridge make manufactured by), with the ratio of 600mL/ minute by the grinding use of embodiment 27~28 Composition is supplied to grinding pad (manufacture of SUPREME RN-H, Nitta Haas Co., Ltd.), carries out grinding for 4 minutes silicon wafers Mill.Used silicon wafer is the P-type semiconductor of a diameter of 300mm, and crystal orientation is (100).As grinding condition at this time, Grinding load is 0.012MPa, and the rotary speed for grinding platen is 40rpm, and the rotary speed of carrier is 39rpm.
These embodiments 27~28 and reference example are carried out with the measure of defect number and haze value.Will be measured the defects of number Table 8 is shown in the result of haze value.Herein, the measurement result of number the defects of reference example and haze value is set as 100 and with opposite Value represents the measurement result of embodiment 27~28.
[table 8]
(evaluation of embodiment)
As embodiment 27~28 it is found that if the use level of abrasive grain included in composition for polishing increases, defect number Increase.It is believed that its reason is:The amount of abrasive grain increases, so as to which the damage suffered by the wafer surface caused by the abrasive grain increases. On the other hand, even if the use level of abrasive grain increases, haze value does not also almost change.
<Evaluation test 9>(embodiment 29~34, comparative example 4)
In embodiment 29, the composition for polishing with the composition for polishing identical component used in embodiment 2 is used Sample 2。
The Sample 21 of embodiment 30 is in addition to by the use level of the polyalcohol (1) of the composition for polishing of embodiment 29 0.007 weight % is set as, is further combined with other than the pool Lip river sand amine of 0.007 weight %, the composition identical with embodiment 29.
The Sample 22 of embodiment 31 is in addition to by the use level of the polyalcohol (1) of the composition for polishing of embodiment 30 0.004 weight % is set as, further the use level for mooring Lip river sand amine is set as other than 0.010 weight %, it is identical with embodiment 30 Composition.
In embodiment 32, the composition for polishing with the composition for polishing identical component used in embodiment 4 is used Sample 4。
The Sample 23 of embodiment 33 is in addition to by the ammonium hydroxide (NH of the composition for polishing of embodiment 304OH) Use level is set as other than 0.50 weight %, the composition identical with embodiment 30.
The Sample 24 of embodiment 34 is in addition to by the ammonium hydroxide (NH of the composition for polishing of embodiment 314OH) Use level is set as other than 0.50 weight %, the composition identical with embodiment 31.
In comparative example 4, the composition for polishing with the composition for polishing identical component used in comparative example 2 is used Sample_CP2。
The ingredient of embodiment 29~34 and the composition for polishing of comparative example 4 is shown in table 9.
For the composition for polishing of above-described embodiment 29~34, comparative example 4 and reference example, with identical with embodiment 4~6 Grinding condition be ground.Also, carry out the measure of defect number and haze value.Will be measured the defects of number and haze value knot Fruit is shown in table 9.Herein, the measurement result of number the defects of reference example and haze value is set as 100 and embodiment is represented with relative value 29~34 and the measurement result of comparative example 4.
[table 9]
(evaluation of embodiment)
If by embodiment 29,30 and comparative example that the sum of polyalcohol (1) and the use level for mooring Lip river sand amine are 0.014 weight % 4 are compared, then it is found that the embodiment 29,30 as the composition for polishing comprising polyalcohol and the comparison without polyalcohol Example 4 is compared, and defect number, haze value significantly reduce.
If the equal embodiment 29,30 of the sum of polyalcohol (1) and the use level for mooring Lip river sand amine is compared, it is found that With without pool Lip river sand amine embodiment 29 compared with, comprising pool Lip river sand amine embodiment 30 the defects of number and haze value reduce.
According to embodiment 31 and 32 it is found that the use level of the pool Lip river sand amine in composition for polishing is more than the reality of embodiment 31 The defects of applying example 32 number and haze value reduce.
By the comparison of embodiment 30 and embodiment 33 and the comparison of embodiment 31 and embodiment 34 it is found that if grinding is used The content of ammonium hydroxide included in composition increases, then defect number and haze value increase.It is believed that its reason is:If hydrogen The amount of amine-oxides increases, then ammonium hydroxide increases the etching power of silicon wafer, and wafer surface generates crude.
It will be understood that this time disclosed implementation form is to illustrate and unrestricted in all respects.The scope of the present invention is simultaneously It is non-to illustrate to represent by above-mentioned implementation form, but represented by claims, it is intended to comprising with claims are impartial contains Being had altered in justice and range.
Industrial availability
The present invention can be used for composition for polishing.

Claims (6)

1. a kind of composition for polishing, it includes:
Abrasive grain,
Selected from at least one of the vinyl alcohol resin of 1,2- diol structure units represented by following formula (1) water solubility Macromolecule,
Polyalcohol and
Alkali cpd,
In formula, R1、R2And R3Separately represent hydrogen atom or organic group, X represents singly-bound or key chain, R4、R5And R6Respectively Independently represent hydrogen atom or organic group, R7And R8Separately represent hydrogen atom.
2. composition for polishing according to claim 1 also includes nonionic surfactant.
3. composition for polishing according to claim 2, wherein,
The nonionic surfactant is the diamine compound represented by the following general formula (2), which includes tool There is the Alkylenediamine structure of 2 nitrogen, and at least one block type polyethers be bonded on 2 nitrogen of the Alkylenediamine structure, And the block type polyethers is that oxygen ethylidene is bonded with oxygen propylidene,
In formula, n represents more than 1 integer.
4. composition for polishing according to any one of claim 1 to 3, wherein,
As the polyalcohol, comprising two or more.
5. composition for polishing according to any one of claim 1 to 3, wherein,
The polyalcohol is the alkylene oxide derivative of methyl glucosamine.
6. composition for polishing according to claim 4, wherein,
The polyalcohol is the alkylene oxide derivative of methyl glucosamine.
CN201680061350.6A 2015-10-23 2016-10-21 Polishing composition Active CN108138032B (en)

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